Liquid-dispersible, polymeric colorant compositions and aqueous dispersions and process for the preparation thereof

ABSTRACT

Disclosed are liquid-dispersible colorant compositions and stable aqueous dispersions of such colorant materials. The colorant is a polymeric colorant comprising a water-insoluble, polymeric colorant comprising a polyester having copolymerized therein residues of one or more monomeric, organic colorant compounds.

This is a divisional application of copending application Ser. No.07/484,333 filed on Feb. 26, 1990 U.S. Pat. No. 5,043,376.

This invention pertains to certain novel, liquid-dispersible colorantcompositions in a finely-divided form comprising (i) a polyester havingcopolymerized therein the residues of one or more colorant compounds and(ii) one or more surfactant compounds. This invention also pertains toaqueous dispersions of the compositions and processes for thepreparation of both the compositions and the dispersions.

An important factor which determines the color strength of a pigment isparticle size and as the pigment particle size is reduced, colorantstrength is increased to a maximum value. For particle sizes greaterthan about 0.5 micron, Mie theory predicts that color strength isinversely proportional to particle diameter, and is approximatelyindependent of refractive index of the particle relative to the mediumand the absorption coefficient of the pigment. Thus, particle size is ofconsiderable importance to the utility and value of pigments.

Various processes for the manufacture of finely-divided forms ofpolyesters have been disclosed in the prior art such as U.S. Pat. Nos.3,586,654, 3,669,922, 3,674,736, 3,931,082, 4,112,215, 4,254,207,4,267,310, 4,305,864, 4,378,228, 4,451,606 and 4,462,839. Some of theseknown processes include the presence of pigments such as carbon blackduring particle size reduction to produce colored polyester powders. Theknown procedures are summarized below.

1. Comminution, as by grinding, which is difficult and expensive andresults in highly irregular-shaped particles having a broad range ofparticle size distribution.

2. Spray drying techniques which tend to produce "hollow shells" orporous particles and also are hazardous when organic solvents are usedto dissolve the polyester.

3. Dispersion processes which involve melting the polymer in an inertsolvent in the presence of a non-ionic dispersing agent. Polyesters, incontrast to other thermoplastic polymers, tend to hydrolyze (decompose)when melted in the presence of water and the particles thus producedhave a strong tendency to agglomerate or coalesce.

4. Heating under shearing agitation conditions a condensation polymer inan aprotic liquid which is not a solvent for the polymer and in thepresence of a dispersing agent to form small liquid particles andcooling with agitation. Colorants added during this process are stillextractable, sublimable, and may exude from the polymer.

5. Solvent induced crystallization wherein an amorphous polymer isinitially contacted with a crystal-inducing fluid under certainconditions while the polymer is subjected to physical and/or ultrasonicforces. Colorants added during this process are not reacted with thepolymer and therefore are subject to removal from the polymer.

6. Producing microcrystalline polyesters by a hydrolytic removal ofamorphous regions of synthetic, linear polyesters followed by amechanical disintegration of the resulting aggregated microcrystals.

7. Crystallization of polyesters in the presence of nucleating agents.

U.S. Pat. No. 4,177,177 discloses a polymer emulsification process butdoes not provide for the preparation of dry powders.

Plastics, paints, printing inks, rubber, cosmetics and similar materialstypically are colored by organic pigments when superior brilliance andtinctorial strength are important. Toxicity considerations have been achronic problem relative to the use of organic pigments since some havebeen shown to be potential carcinogens and to cause contact dermatitis.Plastics usually contain various additives such as fillers,plasticizers, colorants, etc. The polymeric base of such plasticsnormally does not produce allergic or other adverse reactions bythemselves but leachable or extractable additives are known [Fregert,Manual of Contact Dermatitis, Munkaard Denmark (2nd Ed. 1981)] to causecontact dermatitis.

One embodiment of our invention concerns a liquid-dispersible, polymericcolorant composition in the form of a powder comprising an intimatemixture of:

I. a water-insoluble, polymeric colorant comprising a linear,thermoplastic, linear polyester having copolymerized therein at least 5weight percent, based on the weight of component I, of residues of oneor more monomeric, organic colorant compounds; and

II. an ionic, preferably anionic, or amphoteric surfactant.

Component I of the above-described compositions comprise crystalline,semi-crystalline and amorphous polyesters having copolymerized thereinat least 5.0 weight percent of the residues of at least one monomeric,organic colorant compound. The concentration of the colorant residue inthe polyester is dependent on such factors as the end use for which aparticular concentrate is designed, the polyester being used and thephysical characteristics required of the color concentrate. Normally,the polymeric colorant will not contain more than 55 weight percent ofcolorant residues with a concentration in the range of about 10 to 40weight percent being more common. Typically, the polymeric colorantshave an inherent viscosity of at least 0.20 and are comprised of (i) adiacid component consisting of the residues of one or more dicarboxylicacids, (ii) a diol component consisting of the residues of one or morediols and (iii) a colorant component consisting of the residues of oneor more colorant compounds. The concentration of colorant component(iii) and inherent viscosity are interrelated to the extent that thedegree of polymerization and the inherent viscosity should besufficiently high to ensure that substantially all of the colorantcompound is reacted into the polymer and, preferably, into polymerchains which are not extractable. Thus, for example, when theconcentration of colorant component (iii) is 20 weight percent orhigher, the inherent viscosity of the polyester normally will be about0.25 or higher.

The diacid residues may be derived from aliphatic, alicyclic, oraromatic dicarboxylic acids such as terephthalic acid, isophthalic acid,1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,succinic acid, glutaric acid, adipic acid, sebacic acid,1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid and the like.In the polymer preparation, it is often preferable to derive the diacidresidues from an ester-forming derivative of the dicarboxylic acid suchas the dimethyl, diethyl, or dipropyl esters. The anhydrides or acidhalides of these acids also may be employed where practical.

The diol components of the described polyesters may be selected fromethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl1,3-propanediol, 1,4-butanediol, 2,2-dimethyl- 1,3-propanediol,1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-cyclohexanediol,1,4-cyclohexanediol, 1,2-cyclohexanedimethanol,1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,X,8-bis(hydroxymethyl) tricyclo-[5.2.1.0]-decane wherein X represents 3,4, or 5; and diols containing one or more oxygen atoms in the chain,e.g., diethylene glycol, triethylene glycol, dipropylene glycol,tripropylene glycol, 1,3- and 1,4-bis(2-hydroxyethyl)benzene and thelike. In general, these diols contain 2 to 18, preferably 2 to 12 carbonatoms. Cycloaliphatic diols can be employed in their cis or transconfiguration or as mixtures of both forms.

The amorphous polymeric colorants useful in our invention exhibit aglass transition temperature (Tg) and no, or only a trace of,crystallization or melting point by differential scanning calorimetry(DSC). Examples of such amorphous polyesters include those obtained bythe polymerization of a monomeric colorant compound, terephthalic and/or2,6-naphthalenedicarboxylic acid and a branched-chain diol having theformula ##STR1## wherein R¹ is hydrogen or an unsubstituted orsubstituted alkyl, cycloalkyl or aryl radical and R² is an unsubstitutedor substituted alkyl, cycloalkyl or aryl radical. Preferred amorphouspolymeric colorants have an inherent viscosity of about 0.2 to 0.8 andare comprised of:

(i) diacid residues comprised of at least 50, preferably at least 80,mole percent terephthalic and/or 2,6-naphthalenedicarboxylic acidresidues;

(ii) diol residues comprised of at least 50, preferably at least 80,mole percent of residues of a diol having the formula ##STR2## whereinR¹ is hydrogen or lower alkyl and R² is lower alkyl; and (iii) residuesof a monomeric colorant compound. The particularly preferred amorphouspolymeric colorants are comprised of (i) diacid residues consistingessentially of terephthalic and/or 2,6-naphthalenedicarboxylic acidresidues; (ii) diol residues consisting essentially of2,2-dimethyl-1,3-propanediol residues; and (iii) residues of one or moremonomeric colorant compounds.

Other amorphous polyesters, as defined above, suitable for preparing thepolymeric colorants may be obtained by employing (1) two dicarboxylicacids and one or more diols or (2) two diols and one or moredicarboxylic acids according to known procedures for obtaining amorphouspolyesters. The polyester comprising a diacid component consisting of 75mole percent terephthalic acid residues and 25 mole percent1,4-cyclohexanedicarboxylic acid residues, a diol component consistingof 1,4-butanediol residues and residues of methine compound (I) is anexample of such a polyester.

The partially-crystalline polymeric colorants usually exhibit a glasstransition temperature, a crystallization temperature and a meltingtemperature by DSC. These partially-crystalline, polyester colorants arecomprised of (i) diacid residues consisting of at least 80 mole percentterephthalic acid residues, 2,6-naphthalenedicarboxylic acid residues,1,3-cyclohexanedicarboxylic acid residues, 1,4-cyclohexanedicarboxylicacid residues or a mixture thereof, (ii) diol residues consisting of atleast 50 mole percent of residues having the formula --O--(CH₂)_(p)--O-- wherein p is 2, preferably 4, to 12 and (iii) residues of colorantcompound (I). A preferred partially-crystalline polymeric colorant has amelting temperature of at least 110° C. and is comprised of (i) diacidresidues comprised of at least 80 mole percent terephthalic acidresidues, (ii) diol residues comprised of at least 80 mole percent ofresidues of 1,4-butanediol, and (iii) residues of one or more monomeric,colorant compounds. An especially preferred partially-crystallinepolymeric colorant has a melting temperature of at least 110° C. andconsists essentially of (i) terephthalic acid residues, (ii)1,4-butanediol residues and (iii) residues of one or more monomericcolorant compounds.

The monomeric, organic colorant compounds useful in the preparation ofthe polymeric colorants of component I of our novel compositions are nota critical feature of our invention. The essential characteristics ofthe colorant compounds are (1) sufficient thermal stability to permitcopolymerization with the above-described polyesters and (2) thepresence on the structure of colorant compounds of 2 substituents whichare reactive with at least one of the monomers from which the polyestersare prepared. The colorant compounds may be selected from anthraquinone,methine, bis-methine, 3H-dibenzo[f,ij]isoquinoline (anthrpyridone),2,5-diarylaminoterephthalic acid or ester, 2H-1-benzopyran-2-one(coumarin), quinophthalone, perylene and other thermally-stable colorantcompounds. Representative compounds useful in preparing the polymericcolorants employed in the compositions provided by this invention aredescribed in U.S. Pat. Nos. 4,267,306, 4,359,570, 4,403,092, 4,617,373,4,080,355, 4,740,581, 4,116,923, 4,745,173 and 4,804,719. Examples ofthe reactive substituents present on the colorant compounds includehydroxy, carboxy, an ester radical, amino, alkylamino, and the like. Theester radicals may be any radical having the formula ##STR3## wherein R³is selected from the unsubstituted or substituted alkyl, cycloalkyl oraryl radicals. R³ preferably is unsubstituted alkyl, e.g., alkyl of upto about 8 carbon atoms, or phenyl, and most preferably, lower alkyl,e.g., methyl and ethyl.

Examples of the anthraquinone colorants include compounds having theformula ##STR4## wherein

AQ is a 1,5- or 1,8-anthraquinonylene radical, i.e., radicals having thestructure ##STR5##

R¹ is hydrogen or an unsubstituted or substituted alkyl, cycloalkyl oraryl radical; R² are the same or different and are unsubstituted orsubstituted alkyl, cycloalkyl or aryl;

R² is an unsubstituted or substituted alkyl, cycloalkyl or aryl radical;and

X is a group reactive with at least one of the functional groups of themonomers from which the polyester is prepared, i.e., one of the reactivegroups described hereinabove.

Examples of the useful monomeric methine colorants include compoundshaving the formula ##STR6## wherein

A is an aniline, 1,2,3,4-tetrahydroquinoline,2,3-dihydro-1,4-benzoxazine or 2,3-dihydroindole residue of a methinecolorant compound bearing one polyester-reactive substituent; and

B is an unsubstituted or substituted alkoxycarbonyl radical or anaromatic, carbocyclic or heterocyclic radical bearing one polyesterreactive substituent, i.e., a group reactive with at least one of thefunctional groups of the monomers from which the polyester is prepared;provided that the methine colorant compound contains twopolyester-reactive substituents.

The crystallinity of the polymeric colorants prepared as describedherein may be modified by subjecting them to adissolution-crystallization-precipitation procedure wherein theamorphous or partially-crystalline polymeric colorants are dissolved inan organic solvent from which the polymeric colorant is recovered in afinely divided form. Examples of the solvents in which such polymericcolorants may be dissolved include halogenated hydrocarbons, such asaliphatic chlorides, e.g., methylene chloride, esters such as alkylesters of carboxylic acids, e.g., ethyl acetate and methyl benzoate,hydrocarbons such as toluene and ethers such as tetrahydrofuran.Methylene chloride is a particularly effective solvent for use in thedissolution-crystallization-precipitation procedure.

The ionic or amphoteric surfactants constituting component II of thecompositions of our invention may be selected from a wide variety ofknown, commercially-available compounds and compositions. Examples ofthe anionic surfactants include alkali salts of higher fatty acids,e.g., carboxylic acids having about 12 to 24 carbon atoms, especiallysodium stearate; alkali metal and alkaline earth stearoyl lactylatessuch as sodium and calcium stearoyl lactylates; glyceroyl esters such asphosphated mono- and di-glycerides, citric acid esters ofmonoglycerides, diacetylated tartaric acid esters of monoglycerides,sulfonated esters; and alpha tocopherol-hemisuccinate. Examples of theanionic and amphoteric surfactants include soy phosphatides,phospholipids, lysophospholipids, etc. such as mono- and di-acylphosphatidylcholine, phosphatidic acid, phosphatidylserine, phosphatidylethanolamine, etc.

The amount of component II can vary substantially, e.g. from about 0.5to 30 weight percent, preferably about 1.0 to 10 weight percent, basedon the weight of the polymeric colorant. Factors which may be consideredin determining the amount of component II used include the particularpolymeric colorant used, the particular process (described hereinbelow)used to manufacture the composition, the amount, if any, of a nonionicsurfactant (Component III defined hereinbelow) present, the particularend use for which the composition is intended, etc. The surfactantconstituting component II preferably is an anionic surfactant,especially an alkali metal salt of a carboxylic acid having about 16 to20 carbon atoms present in an amount which is about 1.0 to 10 weightpercent based on the weight of the polymeric colorant.

The liquid-dispersible, colorant compositions described above based oncomponents I and II are readily dispersible in oil-based compositions bymilling the composition and an oil-based material, e.g., castor oil,mineral oil, propylene glycol, petrolatum, etc., using conventionalpigment milling equipment such as a three-roll mill or a colloid mill.The particles of the essentially-dry colorant compositions compriseaggregates of generally spherical particles of the polymeric colorantobtained by the process described hereinafter. The spherical particlestypically have an average particle size of about 2 microns or less andcontain the ionic surfactant on the surface thereof.

A second embodiment of our novel liquid-dispersible, colorantcompositions is a powder which contains an additional surfactantmaterial and comprises an intimate mixture of:

I. a water-insoluble, polymeric colorant comprising a linear,thermoplastic, linear polyester having copolymerized therein at least 5weight percent, based on the weight of component I, of residues of oneor more monomeric, organic colorant compounds;

II. an ionic, preferably anionic, or amphoteric surfactant; and

III. a nonionic poly(oxyalkylene) surfactant having an average molecularweight of at least 300, preferably about 1000 to 15,000, having ahydrophobic-lipophobic value of about 10 or greater.

These compositions, which also are comprised of aggregates of small,generally spherical particles of components I, II and III, aredispersible in oils or oil-like materials by conventional millingtechniques.

The nonionic, poly(oxyalkylene) surfactants constituting the surfactantof component III of the colorant compositions defined above are knownmaterials available from several manufacturers under the tradenamesTergitol, Pluronic, Altox, Tween, Myrj, Brij and Rexene. Many of thesepoly(oxyalkylene) compounds may be characterized by formula

    R.sup.4 O--(--alkylene--O--).sub.n --R.sup.5               (III)

wherein R⁴ is hydrogen or alkanoyl, e.g., a carboxylic acid acylresidues containing up to about 30 carbon atoms, preferably about 12 to24 carbon atoms; R⁵ is hydrogen, alkanoyl, alkyl of up to 24 carbonatoms, typically alkyl of about 12 to 18 carbon atoms, cycloalkyl, arylincluding aryl substituted with alkyl of up to about 12 carbon atomssuch as nonylphenyl, or an anhydromonosaccaride residue, e.g., ananhydrosorbitol (sorbitan) residue; the alkylene residue contains 2 toabout 4 carbon atoms, especially ethylene or propylene; and n is thevalue required for a polymer having (i) a molecular weight of about 1000to 15,000 and (ii) a HLB value of 10 or greater. The alkylene-O residuemay consist of the same repeating unit or may be a random or blockmixture of a plurality of repeating units, e.g., combinations ofoxyethylene and oxypropylene units.

The amount of component III employed can vary considerably depending ona number of factors such as the particular polymeric colorant, theparticular process (described hereinbelow) used to manufacture thecomposition, the specific ionic or amphoteric surfactant (Component II),and the amount thereof, used, the particular end use for which thecomposition is intended, etc. Generally, the amount of component IIIwill be in the range of about 0.5 to 50 weight percent based on theweight of the polymeric colorant, with amounts in the range of about 1.0to 20.0 weight percent being more typical.

Typically, the combined weight of Components II and III is about 1.0 to50, preferably about 2.0 to 20 percent, based on the total weight ofComponents I, II and III.

The novel aqueous dispersions provided by this invention may be preparedin accordance with the process described below and comprise a mixtureof:

(1) a water-insoluble, polymeric colorant comprising a linear,thermoplastic, linear polyester having copolymerized therein at least 5weight percent, based on the weight of the polymeric colorant, ofresidues of one or more monomeric, organic colorant compounds;

(2) an ionic, preferably anionic, or amphoteric surfactant; and

(3) water.

Polymeric colorant (1) may comprise from about 4 to 25 weight percent ofthe total weight of the dispersion, i.e., the total weight of (1), (2)and (3) with polymeric colorant concentrations of about 10 to 20 weightpercent (same basis) being more typical. The amount of surfactant (2)present is the same as that described above relative to the polymericcolorant compositions.

The water of the aqueous dispersions may be removed according to knowndrying techniques, e.g., spray drying, freeze drying or pan drying, toobtain the liquid-dispersible compositions described hereinabove. Thetemperature used in the drying operation should be less than the glasstransition temperature or melting temperature, depending on the natureof the polymeric colorant, of the Component I colorant material. Thus,the drying temperature normally will not exceed about 140° C. The drypolymeric composition may be dispersed in various organic liquids asdescribed hereinabove. The liquid medium of choice will depend on theend use for which the dispersion is intended. For example, the polymericcolorant composition may be milled in castor oil for use in a lipstickor in mineral oil for use in a water-in-oil cleansing cream.

The aqueous dispersions of this invention preferably contain a nonionicpoly(oxyethylene) surfactant and therefore the preferred aqueousdispersions comprise a mixture of:

(1) a water-insoluble, polymeric colorant comprising a linear,thermoplastic, linear polyester having copolymerized therein at least 5weight percent, based on the weight of component I, of residues of oneor more monomeric, organic colorant compounds wherein the polymericcolorant has an average particle size of less than 2 microns, preferablyan average particle size of about 0.1 to 1.0 microns;

(2) an ionic, preferably anionic, or amphoteric surfactant;

(3) a nonionic poly(oxyalkylene) surfactant having an average molecularweight of at least 300, preferably about 1000 to 15,000, having ahydrophobic-lipophobic value of about 10 or greater; and

(4) water.

The concentration of colorant (1) and surfactant (2) in the preferreddispersions is the same as that set forth above whereas theconcentration of surfactant (3) is the same as that of Component III ofthe compositions relative to the amount of polymeric colorant present inthe dispersion. The presence of nonionic surfactant (3) improves thestability of the dispersions by preventing, or at least retarding, theaggregation or agglomeration of the particles of polymeric colorants toform larger particles.

The aqueous, polymeric colorant dispersions described above may beproduced by the process of our invention which comprises the steps of:

(1) forming an oil-in-water (o/w) emulsion from water and a solution ofComponent I (polymeric colorant) in a volatile, water-immiscible,organic solvent in the presence of Component II (ionic surfactant) and,optionally, Component III; and

(2) removing from the emulsion of (1) the volatile, organic solvent.

The organic solvent used in Step (1) of our novel process may consist ofone or more water-immiscible organic liquids capable of dissolving thepolymeric colorant employed. The useful solvents or solvent systems haveboiling points less than 100° C., preferably in the range of about 35°to 80° C. Example of such solvents include aliphatic and alicyclichydrocarbons such as n-hexane, cyclohexane, cyclopentane,methylcyclopentane, 2-methylpentane, 3-methylpentane and the like;chlorinated hydrocarbons such as methylene chloride, ethylenedichloride, chloroform and the like; alkyl esters of aliphaticcarboxylic acids such as ethyl acetate; and dialkyl ethers such asdiisopropyl ether. The solvent preferably is an organic solvent systemwhich includes, in addition to one or more water. immiscible organicliquids, a volatile, polar, water-miscible solvent such as acetone andalkanols of up to about 4 carbon atoms. For example, the solvent systemof methylene chloride and isopropanol is particularly useful inconjunction with polymeric colorants based onpoly(2,2-dimethyl-1,3-propanediyl terephthalate). Numerous othersubstantially volatile, water-immiscible solvent systems commonly usedin the coatings industry for dissolving polymeric materials may be usedin the practice of the process described herein.

The concentration of the polymeric colorant in the volatile,water-immiscible solvent may be varied substantially but usually will bein the range of colorant:solvent weight ratio of about 1:20 to 1:2, morecommonly about 1:10 to 1:3. The weight ratio of the solution of thepolymeric colorant to water used in the emulsification step generally isin the range of about 4:3 to 1:3 with a range of about 2:3 beingpreferred.

The ionic surfactant (Component II) and optional nonionic surfactant(Component III) employed in the emulsification operation of Step (1) maybe combined with the water used or with the organic phase, i.e., thesolution of the polymeric colorant. The amounts of Components II and IIIwhich may be used are the same as the amounts of those materialsdescribed above relative to the polymeric colorant compositions andaqueous dispersions. The emulsification in Step (1) may be accomplishedby combining the water with the organic phase while submitting theresulting 2-phase mixture to emulsifying action such as agitation orcomminution. The water may be added to the organic phase or the organicphase may be added to the water, which may contain one or both ofComponents II and III. Although temperature is not critical, theemulsification operation typically is carried out at a temperature ofabout 25° to 40° C.

In Step (2), the emulsion of Step (1) is broken by vaporizingessentially all of the organic phase of the emulsion resulting in a finedispersion of the polymeric colorant in the remaining water. Thevaporization of the organic phase, i.e., the water-immiscible solventand any water-miscible solvent used, is advantageously accomplished bydistillation under reduced pressure, e.g., at pressures of about 100 to650 torr. The aqueous dispersion of the polymeric colorant produced maybe used for the coloration of water-based products or may be dried asdescribed above to obtain the polymeric colorant compositions.

The polymeric compositions, aqueous dispersions and process of ourinvention are further illustrated by the following examples. Theinherent viscosities specified herein are determined at 25° C. using 0.5g of polymer (polyester color concentrate) per 100 mL of a solventconsisting of 60 weight percent phenol and 40 weight percenttetrachloroethane. The melting temperatures are determined bydifferential scanning calorimetry on the first and/or second heatingcycle at a scanning rate of 20° C. per minute and are reported as thepeaks of the transitions. All particle sizes given herein are in micronsand were determined using a Microtrac small particle analyzer (Leeds andNorthrup). Results are reported as the maximum particle size for aparticular volume percent of the total dispersed phase.

REFERENCE EXAMPLE 1

The following materials are placed in a 500-mL three-necked,round-bottom flask:

117.2 g (0.604 mol) dimethyl terephthalate

109.9 g (1.056 mol) 2,2-dimethyl-1,3-propanediol

0.0170 g Ti from a n-butanol solution of titanium tetraisopropoxide

14.19 g (0.030 mol)2,2,-[(9,10-dihydro-9,10-dioxo-1,5-anthracenediyl)diimino]bisbenzoicacid having the structure ##STR7## The flask is equipped with a nitrogeninlet, stirrer, vacuum outlet, and condensing flask. The flask andcontents are heated in a Belmont metal bath with a nitrogen sweep overthe reaction mixture as the temperature is increased to 200° C. and thento 220° C. over 90 minutes. Over the next 30 minutes the temperature isincreased to about 240° C. and then to about 260° C. over the next 30minutes. The temperature is quickly raised (over about 10 minutes) to275° C. and a vacuum is applied until the pressure is reduced to 0.5 mmHg. The polycondensation is completed by heating the flask and contentsat about 275° C. for 75 minutes under a pressure of 0.1 to 0.5 mm Hg.The flask is removed from the metal bath and is allowed to cool whilethe polymer solidifies. The resulting dark red polyester, containing 8.0weight percent of the anthraquinone colorant residue, has an inherentviscosity of 0.37, no melting temperature, a weight average molecularweight of 29,399, a number average molecular weight of 15,636 and apolydispersity value of 1.88.

The polymeric colorant obtained is modified by adissolution-crystallization-precipitation procedure to impartcrystallinity thereto. To ethyl acetate (450 mL) heated to 70° C. isadded the polymeric colorant (90.0 g) with stirring. The temperature isincreased to 85° C. to dissolve the colorant and, after refluxing for 1hour, the temperature is decreased at the rate of 1° C. per minute to25° C. The mixture is stirred for 4 hours at room temperature andallowed to stand overnight to allow precipitation of the polymericcolorant. The precipitate is filtered, washed 3 times with acetone andfiltered after each washing and dried under vacuum at 40° C. The totalmodified polymeric colorant thus obtained is 60.2 g.

REFERENCE EXAMPLE 2

The following materials are placed in a 500-mL three-necked,round-bottom flask:

84.09 g (0.433 mol) dimethyl terephthalate

58.60 g (0.563 mol) 2,2-dimethyl-1,3-propanediol

0.0165 g Ti from a n-butanol solution of titanium tetraisopropoxide

85.14 g (0.208 mol)1,5-bis[(3-hydroxy-2,2-dimethylpropyl)amino]anthraquinone

The flask is equipped with a nitrogen inlet, stirrer, vacuum outlet, andcondensing flask. The flask and contents are heated in a Belmont metalbath with a nitrogen sweep over the reaction mixture as the temperatureis increased to 200° C. and then to 220° C. over 90 minutes. Over thenext 30 minutes the temperature is increased to about 240° C. and thento about 260° C. over the next 30 minutes. The temperature is quicklyraised (over about 10 minutes) to 275° C. and a vacuum is applied untilthe pressure is reduced to 0.5 mm Hg. The polycondensation is completedby heating the flask and contents at about 275° C. for 75 minutes undera pressure of 0.1 to 0.5 mm Hg. The flask is removed from the metal bathand is allowed to cool while the polymer solidifies. The resulting darkred polyester, containing 51.6 weight percent of the anthraquinonecolorant residue, has an inherent viscosity of 0.357, no meltingtemperature, a weight average molecular weight of 22,101, a numberaverage molecular weight of 10,157 and a polydispersity value of 2.18.

The polymeric colorant obtained is modified by adissolution-crystallization-precipitation procedure to impartcrystallinity thereto. To ethyl acetate (500 mL) heated to 70° C. isadded slowly the polymeric colorant (75.0 g) with stirring. Thetemperature is increased to 80° C. and then refluxed for 2 hours withstirring. Heating is discontinued and the mixture is allowed to coolovernight to effect precipitation of the polymeric colorant. Theprecipitate is filtered, washed 4 times with acetone and filtered aftereach washing and dried under vacuum at 40° C. to obtain 58.76 g ofmodified polymeric colorant.

REFERENCE EXAMPLE 3

The following materials are placed in a 500-mL three-necked,round-bottom flask:

108.64 g (0.56 mol) dimethyl terephthalate

75.71 g (0.73 mol) 2,2-dimethyl-1,3-propanediol

0.0170 g Ti from a n-butanol solution of titanium tetraisopropoxide

52.0 g (0.127 mol)1,5-bis[(3-hydroxy-2,2-dimethylpropyl)amino]anthraquinone

The flask is equipped with a nitrogen inlet, stirrer, vacuum outlet, andcondensing flask. The flask and contents are heated in a Belmont metalbath with a nitrogen sweep over the reaction mixture as the temperatureis increased to 200° C. and then to 220° C. over 90 minutes. Over thenext 30 minutes the temperature is increased to about 240° C. and thento about 260° C. over the next 30 minutes. The temperature is quicklyraised (over about 10 minutes) to 275° C. and a vacuum is applied untilthe pressure is reduced to 0.5 mm Hg. The polycondensation is completedby heating the flask and contents at about 275° C. for 75 minutes undera pressure of 0.1 to 0.5 mm Hg. The flask is removed from the metal bathand is allowed to cool while the polymer solidifies. The resulting darkred polyester, containing 30.6 weight percent of the anthraquinonecolorant residue, has an inherent viscosity of 0.47, no meltingtemperature, a weight average molecular weight of 31,169, a numberaverage molecular weight of 16,982 and a polydispersity value of 1.83.

This polymeric colorant (57.2 g) is submitted to adissolution-crystallization-precipitation procedure substantially asdescribed in Reference Example 1 to produce 45.15 g of modifiedcolorant.

REFERENCE EXAMPLE 4

The following materials are placed in a 500-mL three-necked,round-bottom flask:

112.97 g (0.643 mol) dimethyl naphthalene-2,6-dicarboxylate

62.50 g (0.601 mol) 2,2-dimethyl-1,3-propanediol

0.0170 g Ti from a n-butanol solution of titanium tetraisopropoxide

51.66g (0.126 mol)1,5.bis[(3-hydroxy-2,2-dimethylpropyl)amino]anthraquinone

The flask is equipped with a nitrogen inlet, stirrer, vacuum outlet, andcondensing flask. The flask and contents are heated in a Belmont metalbath with a nitrogen sweep over the reaction mixture as the temperatureis increased to 200° C. and then to 220° C. over 90 minutes. Over thenext 30 minutes the temperature is increased to about 240° C. and thento about 260° C. over the next 30 minutes. The temperature is quicklyraised (over about 10 minutes) to 275° C. and a vacuum is applied untilthe pressure is reduced to 0.5 mm Hg. The polycondensation is completedby heating the flask and contents at about 275° C. for 75 minutes undera pressure of 0.1 to 0.5 mm Hg. The flask is removed from the metal bathand is allowed to cool while the polymer solidifies. The resulting darkred polyester, containing 30.4 weight percent of the anthraquinonecolorant residue, has an inherent viscosity of 0.37, no meltingtemperature, a weight average molecular weight of 24,390, a numberaverage molecular weight of 13,046 and a polydispersity value of 1.87.

REFERENCE EXAMPLE 5

The following materials are placed in a 500-mL three-necked,round-bottom flask:

126.1 g (0.65 mol) dimethyl terephthalate

94.6 g (0.91 mol) 2,2-dimethyl-1,3-propanediol

0.0182 g Ti from a n-butanol solution of titanium tetraisopropoxide

33.0 g (0.10 mol) methyl3-[4-[[2-(acetyloxy)ethyl]ethylamino]-2-methylphenyl]-2-cyano-2-propenoatehaving the structure: ##STR8## The flask is equipped with a nitrogeninlet, stirrer, vacuum outlet, and condensing flask. The flask andcontents are heated in a Belmont metal bath with a nitrogen sweep overthe reaction mixture as the temperature is increased to 200° C. and thento 220° C. over 90 minutes. Over the next 30 minutes the temperature isincreased to about 240° C. and then to about 260° C. over the next 30minutes. The temperature is quickly raised (over about 10 minutes) to275° C. with a stream of nitrogen bleeding into the system and a vacuumis applied until the pressure is reduced to 0.5 mm Hg. Thepolycondensation is completed by heating the flask and contents at about275° C. for about 1.25 hours under a pressure of 0.1 to 0.5 mm Hg. Theflask is removed from the metal bath and is allowed to cool while thepolymer solidifies. The resulting high molecular weight yellowpolyester, containing 18.1 weight percent of the methine colorantresidue, has an inherent viscosity of 0.20, no melting temperature, aweight average molecular weight of 13,732, a number average molecularweight of 8773 and a polydispersity value of 1.56.

The polymeric colorant obtained is modified by adissolution-crystallization-precipitation procedure to impartcrystallinity thereto. To ethyl acetate (450 mL) heated to 70° C. isadded the polymeric colorant (90.0 g) with stirring. The temperature isincreased to 85° C. to dissolve the colorant and, after refluxing for 1hour, the temperature is decreased at the rate of 1° C. per minute to25° C. The mixture is stirred for 4 hours at room temperature andallowed to stand overnight to allow precipitation of the polymericcolorant. The precipitate is filtered, washed 3 times with acetone andfiltered after each washing and dried under vacuum at 40° C. The totalmodified polymeric colorant thus obtained is 60.2 g.

REFERENCE EXAMPLE 6

The procedure described in Reference Example 5 is repeated using thefollowing materials:

131.4 g (0.68 mol) dimethyl terephthalate

94.6 g (0.91 mol) 2,2-dimethyl-1,3-propanediol 0.0180 g Ti from an-butanol solution of titanium tetraisopropoxide

17.8 g (0.54 mol) methyl3-[4-[[2-(acetyloxy)ethyl]ethylamino]-2-methylphenyl]-2-cyano-2-propenoate

The dark yellow polyester obtained contains 10.0 weight percent of themethine colorant residue, has an inherent viscosity of 0.59, a weightaverage molecular weight of 41,296, a number average molecular weight of22,421 and a polydispersity value of 1.84.

The polymeric colorant is modified by thedissolution-crystallization-precipitation described in Reference Example1 to obtain 81.2 g of modified product.

EXAMPLE 1

To a solution of the polymeric colorant (62.0 g) of Reference Example 1in a mixture of methylene chloride (300.0 g) and isopropanol (100 g) at25° C. are added a poly(oxyalkylene)glycol having an average molecularweight of 3500 and a HLB value of 26.1 (5.5 g; Tergitol XH) and sodiumstearate (1.0 g). Water (600 0 g; 25° C.) is added drop-wise to thepolymeric colorant solution at 25° C. over a period of 15 minutes whilesubjecting the mixture to comminuting force using a Ross homogenizer toform an oil-in-water emulsion. The emulsion is transferred to alaboratory Rotovap apparatus and the methylene chloride and isopropanolare removed at 40° C. and 100-650 torr to yield a latex-like colloidaldispersion of the polymeric colorant which is stable for several days.If any settling occurs after sitting for several weeks, the colorant maybe redispersed by agitation. The solids content (determinedgravimetrically) of the aqueous dispersion is approximately 14 weightpercent and the particle sizes and distribution of the emulsion and thedispersed colorant are:

    ______________________________________                                                     % Relative                                                                            Particle                                                              Volume  Size                                                     ______________________________________                                        Emulsion       10        0.44                                                                50        0.89                                                                90        1.80                                                 Dispersion     10        0.45                                                                50        1.09                                                                90        2.25                                                 ______________________________________                                    

The average particle size of the dispersion is about 1 micron.

If the above-described procedure is modified by dissolving the polymericcolorant in the methylene chloride and then adding the isopropanol,poly(alkylene glycol) and sodium stearate to the colorant solutionfollowed by emulsification as described, the particle sizes anddistribution of the resulting emulsion are:

    ______________________________________                                               % Relative                                                                            Particle                                                              Volume  Size                                                           ______________________________________                                               10      0.55                                                                  50      2.89                                                                  90      8.01                                                           ______________________________________                                    

Thus, the solvent system selected to dissolve the polymeric colorant isimportant to achieving the smallest particle sizes.

EXAMPLE 2

To a solution of the polymeric colorant (5.4 g) of Reference Example 1in a mixture of methylene chloride (25.95 g) and isopropanol (8.65 g) at25° C. is added Tergitol XH surfactant (0.54 g). The resulting solutionis added with vigorous stirring to water (60.0 g; 25° C.) containing adispersion of sodium stearate (0.1 g). Immediately thereafter, themixture is treated with ultrasound for 1 minute at a temperature notgreater than 40° C. using a Branson, Model 184V, ultrasonic device. Theemulsion is transferred to a laboratory Rotovap apparatus and themethylene chloride and isopropanol are removed over a temperature of25°-40° C. and a pressure of 100 to 650 torr. The polymeric colorantdispersion thus obtained is passed through a 230 mesh screen to removeany polymeric colorant not emulsified. The solids content (determinedgravimetrically) of the aqueous dispersion is 6.8 weight percent and theparticle size distribution of the dispersed colorant is:

    ______________________________________                                               % Relative                                                                            Particle                                                              Volume  Size                                                           ______________________________________                                               10      0.43                                                                  50      0.97                                                                  90      3.53                                                           ______________________________________                                    

EXAMPLE 3-6

The procedure described in Example 2 is repeated 3 times substituting0.54 g of the following nonionic surfactants for the Tergitol XHpoly(oxyalkylene glycol:

    ______________________________________                                        Example   Nonionic Surfactant                                                 ______________________________________                                        3         Tween 60, an ethoxylated sorbitan mono-                                       stearate having an average molecular                                          weight of 1310 and a HLB value of 14.9.                             4         Pluronic F127, a poly(oxyethylene/oxy-                                        propylene)glycol block copolymer having                                       an average molecular weight of 12,500 and                                     an HLB value of 22.0.                                               5         Tween 21, an ethoxylated sorbitan mono-                                       stearate having an average molecular                                          weight of 606 and a HLB value of 13.3.                              ______________________________________                                    

In Example 6, the procedure of Example 2 is repeated except that nononionic surfactant is used. The particle sizes and particle sizedistribution of the polymeric colorant in and the solids content (weightpercent) of the aqueous dispersions obtained are set forth in Table I.

                  TABLE I                                                         ______________________________________                                                 Particle Size  Solids                                                Example    10%    50%        90%  Content                                     ______________________________________                                        3          0.46   1.18       3.15 10.0                                        4          0.50   1.78       3.86 7.7                                         5          2.23   6.70       12.90                                                                              8.0                                         6          0.48   2.33       6.69 4.7                                         ______________________________________                                    

In Examples 5 and 6, during measurement the particle size increases withtime, indicating particle agglomeration. Examples 3.6 demonstrate theadvantages with respect to particle size of using a preferred nonionicsurfactant. However, all of the dispersions prepared are useful for oneor more of the purposes described hereinabove.

EXAMPLE 7

A solution of the polymeric colorant (5.3 g ) of Reference Example 5 andTergitol XH (0.53 g) in a mixture of methylene chloride (25.5 g) andisopropanol (8.5 g) at 25° C. is added slowly with vigorous stirring towater (60 g) containing sodium stearate (0.1 g) dispersed therein byultrasonic means. Immediately thereafter, the mixture is treated withultrasound for 1 minute at a temperature not greater than 40° C. using aBranson, Model 184V, ultrasonic device. The emulsion is transferred to alaboratory Rotovap apparatus and the methylene chloride and isopropanolare removed at a temperature not greater than 40° C. and a pressure of100-650 torr. The polymeric colorant dispersion thus obtained is passedthrough a fritted-glass filter to remove any unemulsified polymericcolorant present before particle size measurement. The solids content ofthe aqueous dispersion is 10.7 weight percent and the particle sizes anddistribution of the dispersed colorant are:

    ______________________________________                                               % Relative                                                                            Particle                                                              Volume  Size                                                           ______________________________________                                               10      0.20                                                                  50      0.69                                                                  90      2.56                                                           ______________________________________                                    

The average particle size of the dispersion is 1.1 microns.

EXAMPLE 8

The procedure described in Example 7 is repeated except that theTergitol XH is omitted. The particle size distribution of the resultingpolymeric colorant dispersion is:

    ______________________________________                                               % Relative                                                                            Particle                                                              Volume  Size                                                           ______________________________________                                               10      1.72                                                                  50      5.39                                                                  90      9.95                                                           ______________________________________                                    

Repeated particle size measurements show that the particle sizeincreases with time, indicating particle agglomeration. The solidscontent of the dispersion, determined gravimetrically, is 9.7 weightpercent.

EXAMPLE 9

The procedure of Example 8 is repeated using as the organic phase 40.0 gof a solution of the polymeric colorant of Reference Example 2 (50.0 g)in methylene chloride (420 g) and isopropanol (80.0 g) with Tergitol XH(0.36 g) dissolved in the 40 g portion. The solids content of theaqueous dispersion obtained is 7.5 weight percent and the particle sizedistribution of the dispersed polymeric colorant is:

    ______________________________________                                               % Relative                                                                            Particle                                                              Volume  Size                                                           ______________________________________                                               10      0.14                                                                  50      0.33                                                                  90      1.32                                                           ______________________________________                                    

Average particle size is 0.51 micron.

EXAMPLE 10

This example demonstrates the preparation of a dispersion wherein aphase inversion occurs in the preparation of the intermediate emulsion.

To a solution of the polymeric colorant (50.0 g) of Reference Example 6and Tergitol XH (5.0 g)in a mixture of methylene chloride (300.0 g) andisopropanol (100 g) at 25° C. is added slowly water having sodiumstearate dispersed therein (1.0 g sodium stearate in 600 g water) bymeans of a Ross homogenizer while subjecting the mixture to thecomminuting force of a Ross homogenizer. At the phase inversion,indicated by a sudden decrease in viscosity, water addition is stopped.The amount of the aqueous sodium stearate dispersion added is 325 g. Theemulsion thus produced is transferred to a laboratory Rotovap apparatusand the methylene chloride and isopropanol are removed at 35° C. and100-650 torr. The aqueous dispersion is filtered through a 325 meshscreen. The solids content is 11.9 weight percent and the particle sizedistribution of the dispersion is:

    ______________________________________                                               % Relative                                                                            Particle                                                              Volume  Size                                                           ______________________________________                                               10      0.45                                                                  50      0.96                                                                  90      2.28                                                           ______________________________________                                    

EXAMPLE 11

The procedure of Example 10 is increased in scale by a factor of 3.5.The solids content of the dispersion obtained is 13.7 weight percent andthe particle size distribution of the polymeric colorant is:

    ______________________________________                                               % Relative                                                                            Particle                                                              Volume  Size                                                           ______________________________________                                               10      0.44                                                                  50      0.91                                                                  90      2.26                                                           ______________________________________                                    

EXAMPLE 12

The procedure of Example 10 is repeated using a solution of thepolymeric colorant (50.0 g) of Reference Example 3 and Tergitol XH (5.0g) in a mixture of methylene chloride (240.0 g) and isopropanol (80 g).The amount of the aqueous sodium stearate dispersion used to make theemulsion is 289 g. Particle size is measured after most of the organicsolvent has been removed (solids content of 14.0 weight percent) andagain when all of the organic solvent and some of the water has beenremoved to increase the solids content of the dispersion to 23 weightpercent. The particle size distribution is:

    ______________________________________                                        Solids     Particle Sizes                                                     Content    10%           50%    90%                                           ______________________________________                                        14         0.43          0.98   2.46                                          23         0.53          1.64   4.32                                          ______________________________________                                    

COMPARATIVE EXAMPLE 1

The procedure of Example 8 is repeated except that the sodium stearateis replaced with a poly(oxyethylene) 300-caprylic/capric glyceridecomposition (1.0 g; Softigen 767-Huls America, Inc.) having an averagemolecular weight of approximately 500 and a HLB value of 19. Immediatelyafter the comminuting force is removed from the organic/aqueous mixture,the 2 phases separate. This example demonstrates the importance of theionic or amphoteric surfactant.

COMPARATIVE EXAMPLE 2

To a solution of the polymeric colorant (50.0 g) of Reference Example 1in a mixture of methylene chloride (240.0 g) and isopropanol (80.0 g) at25° C. is added poly(oxyethylene) 20 sorbitan monostearate (5.0 g; Tween60). Water (600 g) having glyceryl monostearate (1.0 g: Myvaplex 600having an HLB value of 2.8) dispersed therein by means of a Ross mixeris added slowly to the solution of the polymeric colorant whilesubjecting the mixture to the comminuting force of a Ross mixer. Thereis no evidence of phase inversion and when the comminuting force isstopped the organic phase immediately separates from the aqueous phase.

EXAMPLE 13

This example demonstrates the use of the aqueous dispersion of polymericcolorant prepared in Example 9 in a oil-in-water lotion.

The following ingredients constituting the oil phase are heated to 80°C.:

10.0 g Myvatex Texturelite emulsifier

25.0 g Myverol glyceryl monostearate

20.0 g Emersol 132 fatty acids

10.0 g Arlacel 165 nonionic emulsifier

17.0 g Isopropyl palmitate

17.0 g Drake Oil No. 9 mineral oil

10.0 g Dow Corning 200 silicone oil

The following ingredients constituting the water phase are blendedtogether and heated to 80° C.:

831.7 g Deionized water

20.0 g Germaben IIE

10.0 g Propylene glycol

The oil phase (80° C.) is mixed into the water phase (80° C.) using ahigh shear mixer to make an oil-in-water emulsion and then is allowed tocool while adding the remaining ingredients. The aqueous dispersion ofpolymeric colorant (7.3 g, at 25° C.) is added to the oil in-wateremulsion (at 60° C.) with continued high shear mixing. Vitamin E (10.0g) and fragrance (2.0 g) are added to and stirred in the emulsion (at50° C.). The entire mixture is mixed with a propeller mixer until thetemperature reaches 32° C. The aqueous dispersion of the polymericcolorant imparts a very bright yellow color to the lotion.

EXAMPLE 14

The aqueous polymeric dispersion (40 g) prepared in Example 12 isstirred into 60 g of an aqueous dispersion (32% solids) of awater-dispersible, sulfonate-containing, linear polyester (EASTEKpolyester polymer) containing Acrylsol RM-825 viscosity modifier (1 g;Rohm & Haas). The mixture is homogeneous and the polymeric colorantparticles remain suspended for several days. A drawdown (No. 2 RKdrawdown rod on coated paper) of the mixture results in a smooth,homogeneously-colored, ink film.

EXAMPLE 15

The aqueous dispersion of polymeric colorant prepared in Example 11 isspray dried using an APV Anhydro A/S spray dryer, equipped with acentrifugal atomizer, at an inlet temperature of 30° C., an outlettemperature of 40° C. and a spray rate of 6.9 mL per minute. The dry,polymeric colorant composition is dispersed by adding water and shaking.The particle size distribution of the polymeric colorant particles isfound to be:

    ______________________________________                                               % Relative                                                                            Particle                                                              Volume  Size                                                           ______________________________________                                               10       5.25                                                                 50      11.24                                                                 90      19.56                                                          ______________________________________                                    

The dry, polymeric colorant composition (20.0 g) is milled in castor oil(46.67 g) on a 3-roll mill for 3 passes and the fineness of the grind ofthe milled composition is determined on a NPIRI gage which shows thatall particles of the polymeric colorant composition are 4 microns orless.

EXAMPLE 16

The aqueous dispersion of polymeric colorant prepared in Example 12 isspray dried as described in Example 15 using an inlet temperature of140° C., and outlet temperature of 84° C. and a spray rate of 39 mL perminute. The dry, polymeric colorant composition is milled in castor oilas described above to give a composition in which the particles of thepolymeric colorant composition are 4 microns or less.

The castor oil dispersions of the dry, polymeric colorant compositionsof Examples 11 and 12 are intimately mixed using a spatula on a glassplate with titanium dioxide in a dispersion:TiO₂ weight ratio of 3:1 todetermine the color strength of the colorant compositions. The colorstrength of each colorant composition is found to be significantlygreater than that of the powders of the polymeric compositions of thereference examples prepared by crystallization and grinding, e.g., byjet milling or cryogenic hammer milling.

EXAMPLE 17

The aqueous dispersions prepared in Examples 7 and 8 are air dried in analuminum pan under ambient conditions. Each of the dry, polymericcolorant compositions (0.5 g) is milled in castor oil (1.0 g) on aHoover muller (Hoover Color Corporation) for 8×50 revolutions with 150pounds force. Each mixture then is intimately mixed using a spatula on aglass plate with titanium dioxide (3:1 weight ratio castor oildispersion to titanium dioxide) to determine the color strength of thecolorant compositions. The color strengths of the 2 colorantcompositions is approximately the same and both possess significantlygreater color strengths than do powders of the polymeric colorant ofReference Example 5 prepared by crystallization and grinding.

EXAMPLE 18

Tergitol XH surfactant (0.40 g) is dissolved in a solution of thepolymeric colorant (4.0 g) of Reference Example 4 in a solvent systemconsisting of methylene chloride (30 g) and isopropanol (6 g) and theresulting solution is added slowly to a vigorously stirred dispersion ofsodium stearate (0.10 g) in water (60 g). The resulting emulsion istreated with ultrasound to make fine particles and then the organicsolvents are removed by distillation under reduced pressure at atemperature below 35° C. as described in the preceding examples. Theaqueous dispersion of polymeric colorant (solids content=8.9 weightpercent) produced is passed through a coarse fritted-glass filter priorto particle size measurement. The particle size distribution is:

    ______________________________________                                               % Relative                                                                            Particle                                                              Volume  Size                                                           ______________________________________                                               10      0.16                                                                  50      0.44                                                                  90      0.91                                                           ______________________________________                                    

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. Process for the preparation of an aqueous dispersion of awater-insoluble, polymeric colorant comprising a thermoplastic, linearpolyester having copolymerized therein at least 5 weight percent, basedon the weight of the polymeric colorant, of residues of one or moremonomeric, organic colorant compounds wherein the polymeric colorant hasan average particle size of less than 2 microns comprising the stepsof:(1) forming an oil-in-water emulsion from water and a solution of thepolymeric colorant in a volatile, water-immiscible, organic solvent inthe presence of (i) an ionic or amphoteric surfactant and (ii) anonionic poly(oxyalkylene) surfactant having an average molecular weightof at least 300 and a hydrophobic-lipophobic balance value of about 10or greater; and (2) removing from the emulsion of (1) the volatile,organic solvent.
 2. Process for the preparation of an aqueous dispersionof a water-insoluble, polymeric colorant comprising a linear,thermoplastic, linear polyester having copolymerized therein about 10 to40 weight percent, based on the weight of the polymeric colorant, ofresidues of one or more monomeric, organic colorant compounds whereinthe polymeric colorant has an average particle size of less than 2microns comprising the steps of:(1) forming an oil-in-water emulsionfrom water and a solution of the polymeric colorant in a volatile,water-immiscible, organic solvent in the presence of:(i) about 1.0 to 10weight percent, based on the weight of the polymeric colorant, of analkali metal salt of a carboxylic acid having about 12 to 24 carbonatoms; and (ii) about 1.0 to 20.0 weight percent, based on the weight ofthe polymeric colorant, of a nonionic poly(oxyalkylene) surfactanthaving an average molecular weight of about 1000 to 15,000 and ahydrophobic-lipophobic balance value of about 10 or greater; ; and (2)removing from the emulsion of (1) the volatile, organic solvent.
 3. Anaqueous dispersion according to claim 2 wherein the concentration of thepolymeric colorant is about 10 to 20 weight percent based on the totalweight of the dispersion.